Dyesttjff derived from indoline bases and process of preparing same



Reissued Mar. 7, 1933 UNITED STATES PATENT OFFICE OTTMAR WAHL, OF LEVERKUSEN, GERMANY; ASSIGNOR TO GENERAL ANILINE WORKS, INC., OF NEW YORK, N. Y., A CORPORATION OF DELAWARE DYESTUFF DERIVED FROM INDOLINE BASES AND PROCESS OF PREPARING SAME N0 Drawing. Original N0. 1,755,678, dated April 22, 1930, Serial No. 186,829, filed April 26, 1927.

Application for reissue filed February 20, 1932.

The present invention relates to new dyestufl's derived from indoline bases and a process of preparing same.

I have found that by treating a 1.3.3-tr alkyl-Q-methylene indoline (such as 1.3.3-tr1- methyLQ-methylene indoline) of the formula:

alkyl all:

wherein the benzene nucleus may be substituted or not or a salt thereof of the formula:

alkyl i a1kyl N/ CH| I alkyl wherein the benzene nucleus may be substituted or not and 00 stands for an organic or inorganic acid ra-dicle with an ester or a salt of nitrous acid in the presence of an organic acid anhydride, as for example acetic anhydride which serves as a condensing agent, there are produced new yellow to orange-red dyestuffs, which correspond probably to the general formula:

wherein the benzene nuclei may be substituted or not and :0 stands for an organic or inorganic acid radicle.

The new dyestuffs are yellow to orange-red crystalline powders soluble in water with light yellow to orange-red color. They dye natural and artificial silk and cotton when Serial No. 594,383.

using tannin or other mordants, in beautiful greenish yellow to reddish-orange shades of good fastness to light.

The following examples will illustrate my invention, all parts being by weight:

Example 1.-Onepart of 1.3.3-trimethyl- Q-methylene indoline (see Berichte der Deutschen Chem. Gese-llschaft, volume 23, page 2630, volume 31, page 612 and page 614) is dissolved in at least 1 part of acetic acid anhydride and 2 parts of sodium nitrite are gradually added with stirring. The solution soon becomes intensely yellow colored, which process may be accelerated by heating. When the indoline has disappeared, the re action mass is run into water in order to destroy the acetic acid anhydride, and the dyestuff is salted out with sodium chloride and zinc chloride, if necessary, with the addition of sodium bisulfite, in order to destroy theexcess of sodium nitrite. The new dyestuff has probably the formula:

It is a clear, greenish-yellow body, which dyes natural and artificial silk and cotton when using tannin or other mordants, in beautiful greenish-yellow shades of good fastness to light, to acids and to alkalies. Instead of sodium nitrite for example, amyl nitrite can be employed; the reaction can also be carried out in the presence of a solvent.

Example 2.1 part of 5-amido-1.3.3-trimethyl-Q-methylene indoline are mixed with 1 part of powdered dry sodium nitrite and the mixture is slowly brought into 2 parts of acetic acid anhydride while stirring. Stirring is continued until the indoline has disappeared, then the reaction mass is run into water and the dyestufl, which dissolves in 90 water with yellow-red color is salted out. It

yellow to reddish-yellow shades of good fast-- wherein m stands for an organic or inorganic acid radical.

' It is in a dry state an orange-red crystalline powder, easily soluble in water and diluted acids. It dyes natural and artificial silk and cotton when using tannin asmordant in reddish-yellow shades of quite good fastnessto light. a 4

I wish it to be understood that inthe following claims one may use instead of a salt of the nitrous acid also an ester of the nitrous acid, and instead of a 1.3.3-trialkyl-2-methylene indoline a salt thereof.

I claim: 4

1. The process which consists in reacting with a salt of nitrous acid upon a 13.3-

trialkyl-Q-methylene indoline of the general formula:

alkyl (Jalkyl N :CH:

a lkyl wherein the benzene nucleus may be substituted in the presence of acetic acid anhydrlde. 2. The process which consists in reacting with sodium nitrite upon 5-amino- 1.3.3-trimethyl-Q-methylene indoline of the probable formula:

N :CHI

in the presence of acetic acid anhydride.

3. As new products dyestufl's corresponding probably to the general formula:

alkyl wherein the benzene nuclei may be substituted or not and 0: stands for an organic or inorganic acid radicle,which are in a dry state yellow to orange-red crystalline powders, soluble in water with light yellow to V orange-red color, and which dye natural and artificial silk and cotton when using tannin or other morda'nts' in beautiful greenish- As newff pi'oducts the dyestuffs corresponding probably to the general formula:

wherein a stands for an organic or inorganic acid radicle and wherein the benzene nuclei may be substituted,said products being in the dry state yellow to orange-red crystalline powders, soluble in water withlight yellow to orange-red color, and which dye natural and artificial silk and cotton,'when using tannin or other mordants beautiful greenishyellow to reddish-yellow shades of good fastness to light.

5. As a new product a dyestufi corresponding probably to the general formula:

:H, mo LIIH CUHx 11,o t NH oH, oo a L to orn z I OH: CH:

wherein m stands for an organic or inorganic acid radicle, which is in a dry state an orangered crystalline powder, easily soluble in water and diluted acids, and which dyes natural and artificial silk and cotton when using tannin as a mordant in reddish-yellow shades of 'quite good fastness to light.

In testimony whereof I aflix my signature.

OTTMAR WAHL, 

